Vitreous compositions consisting of oxides of alkali metal, phosphorus, and other selected divalent metal



Feb. 27, 1945. c. s. KING 2,370,472

- VITREOUS COMPOSITIONS' CONSISTING 0F OXIDES OF ALKALI METAL,

PHOSPHOROUS, AND OTHER SELECTED DIVALENT METAL l /MZ M120 "\/4LKAL/ METAL OX/DE 50c/71 as /Va20 NY M Mm' Fe or' M i Wwuw l y ffgliy Feb. 27, 1945. c. s. KING 2.370,472

VITREOUS COMPOSITIONS CONSISTING OF OXIDES QF ALKALI. METAL, PHOSPHOROUS, AND OTHER SELECTED DIVALENT METAL Fledpot. '7. 1940 3 Sheets-Sheet 2 [L (Nasf/o) :.50 SEGUES 779,4 7/0/V L# 3.00 n 25o 1.50 E L* .00 V5 k1 I' y Q 0150 wf@ l l l L Feb. 27, 1945. C, s KING 2,370,472

' VITREOUS COMPOSITIONS -CONSISTNG-OF OXIDES OF ALKALI METAL,

PHOSPHOROUS, AND OTHER SELECTED DIVALENT METAL Filed OGb. 7, 1940 3 Sheets-Sheet 2 4 e a lo 2 I4 le la 2e sa MOL/M? PERCENT M30 y Patented Feb. 2?, 1945 OXIDES 0F ALKALI METAL, PHOSPHORUS,

AND OTHER. SELECTED DIVALENT METAL Charles S. King, Joliet, lll., assigner to Blockson Chemical Oo., Joliet, Ill.,

nois

a corporation o! Illi- Application October 7, 1940', Serial No. 360,065

The present invention relates to new chemical glass systems useful inthe treatment o1 water, andA to new chemical agents for the treatment of water and for other uses.

In particular, it relates to improvements in an artheretotore known, and to new methods and agents for said art. The treatmentof water refers broadly to city supplies, boiler waters, waters for domestic uses, as for washing dishes and clothes, bathing and other purposes, and in general yit relates to the hardness in such waters.

There is extensive knowledge and practice in the use of alkali metal polyphosphates to treat water.- Reference is made to the following'U. S. patents: Hall, No. 1,956,515, reissued as Re. 19,719, Hall No. 2,035,652, Rosenstein, No.

2,038,316, reissued twice as Re. 20,360 and Re 20,754, and other U. S. patents, such as No. 2,156,173 to Bird, and No. 2,059,570 to Fiske, Warren and Bryan.

As a result of prior developments it is known that the water-soluble vitreous glasses comprising sodium oxide (Naso) and phosphorus pentoxide (P205) have valuable properties in treating water. The present invention relates to that portion of the prior art eld which involves polyphosphates,

.80 improvements in such properties.

chiometrically equivalenti@ the quantity o! in# hibiting agent used.

The prior art vitreous phosphates for such purposes are most commonly dissolved in water and the solutionis then employed, or the solid compound is dissolved in all water to be treated. The

agents have a high total solubility in water, and,` dissolve readily. Granular masses oi the. agent` congeal on being wetted, due to a' high hydro the utility of such agents, not in the chemical functioning, but in the mechanical procedures of using the agent. Also, they are quite unstable in solution at higher temperatures, limiting their eiiiciency in certain uses, as well as their utility.

The present invention aims to provide new agents which overcome one or more defects of these prior-art agents while having their valuable water-treating properties, and in some cases with.

It is an object of the invention to produce new chemical compositions oi' more complex nature for use as 'a substitute for such prior art treating agents, whereby new properties are exhibited, and

a5 whereby properties characterizing the prior art and only the pertinent part of that field will be discussed for the purpose of explaining the present invention. One of the functions of the vitreous products is to sequester" vcalcium and magnesium from waters containing them. Another function of them is designated inhibition l sequestration is the action of an'agent which appears to render the calcium and magnesium content of the waters inert to reaction with soap. sequestration in the prior art is believed to be the result of a reaction whereby the calcium or magnesium cations combine with the dissolved Nazo- A P205 polyphosphate to incorporate the calcium or magnesium into an anion radical, wherein itis inert to react with soap, and other agents which normally react with calcium cations, such as silicates, carbonates, phosphates and sulfate'salts.

. Inhibition in the prior art is the action of a. very small quantity of dissolved Naso-P205 polyphosphate to prevent the precipitation of solid products from the original calcium or magnesium compounds in the waters. A

Whereas sequestration involves stoichiometrical amounts of thetreating phosphate and of the f new agents of the type referred `to with controlled compositions are enhanced. or diminished in desired directions.

Another object oi' the invention is to Produce 80 propertiesdependent upon composition.

It is also an object of the invention to produce chemical glass systems which are polyphosphate -salts comprising oxides of alkali metal and of metal from the group consisting of alkali-earth A metals, magnesium, trivalent iron, and aluminum, regardless of the practical suitability for watertreating by methods practiced heretofore with alkali metal polyphosphates.

A particular object is to produce complexesof decreased hygroscopicit, increased stability, slower rate of solution, and non-congealing permanent granular form. without any substantial' loss in value as water-treating agents. i

It 'is stm another object of the inventionto produce a granular agent for treating water, such that the wa'ter to be treated may ilow throughs bed of the agent toeiect the .desiredA treatment,

"hardness impurities in the water, inhibition does not. Rather, it advantageously inhibits the precipitation of much more material than is stoi- 5B groscopicity 0I the agent.

` duce a granular without use of excess of the agent, and without detrimental change in the porosity oi the bed resulting from the actionl of the water on the agent.

Stillanother object of the invention is to pro-- water-treating agent which may be used as a component ot a dry mix without detriment toy the mix scopic nature. The hygroscopic character limits through ,undesired hy- .These are polymers.

It is a general object of the invention to produce polyphosphate water-treating agents which incorporate alkali metal oxide and another metal oxide of kind and quantity selected for the particular properties which it may produce.

It is a particular object of the invention to produce new polyphosphate water-treating agents having alkali metal oxide and oxide of metal from the group consisting of magnesium, the alkali-earth metals, trivalent iron, and aluminum, said selected metal being herein referred to for convenience as M.

Various other and ancillary objects and advantages of the invention will become apparent I that of Fig. 2 where the alkali metal is sodium, and where the third oxide is of magnesium.

Figs. 4, 5 and 6 are graphs for the sodiummagnesium polyphosphates. showing respectively the properties referred to as hygroscopicity, se-

* questration, and inhibition.

Fig. 'I is a graph comparing the hygroscopicities of sodium-M-polyphosphates where the metal M is varied.

Fig. 8 is a graph showing the solubility of a` certain series of glasses as 'they are aiected by content of MEO.

SODIUM POLYPHOSPHATES The art referred to has developed largely with the sodium polyphosphates. The metal-phosphate compounds are not of simple character like l many other metal salts, and the actual character of the substance is not indicated by its simplest empirical formula. In order to predicate the invitreous and accepted as having-valuable properties for treating water for sequestration and inhibition.

Within the described system of sodium polyphosphates there are known definite compounds, the more common one's being'shown in Table l.

Table 1 Moles of Moles oi NaPos Namo: Forum Name 5 i NaP1On Sodium heptapolyphosphate 4 l NagPOn Sodium hexppolyphosphate 2 1 NaePOn Sodium tetrapolyphospbate 1 l NasPaOm Sodium tripolyphospnatc 'I'hese polyphosphates likewise form polymers. As the general rule in the art, only those polymers of polyphosphates which result from quickly cooling the melted material have value as water-treating agents. They must be vitreous, with the exception that crystalline sodium tripolyphosphate may be used (see U. S. No. 2,174,614).

SODIUM PoLYPHosPnATEs As WATER-TREATING ,AGENTS The effectiveness of the vitreous sodium poly phosphates is determined also by the temperature of the melt which is quickly cooled. I'he 'diii'erent identifiable polyphosphates do not respond identically to the variations in fusion temperature. I have determined the sequestering value of several polyphosphates made at varying fusion temperatures, and then quickly chilled to a glass. The variation is shown in Fig. 1 in which the temperature of the'fusion is plotted horizontally, `and the sequestering property is plotted vertically as parts by weight of calcium A chloride (CaClz) sequestered by 1 part by weight vention later to be described, a .brief reference to the nature of metal phosphates is lin'order, and is given below in connection with the prior art sodium polyphosphates.

The sodium polyphosphates as herein referred to in this art, are molecularly dehydrated phosphates varying from the ratio 1Na2O to lPzOs to the ratio 2Na20 to lPzOs, or in other words varying within the system: phosphate (NaPOs) to sodium pyrophosphate -(Na4P2O'1).

Sodium polyphosphatesj within vthis system form glasses by melting and cooling. The actual character of a glass, for example of NaPOa, varies by polymerization, so that distinctive forms are known, having distinctive properties. Polymerization and depolymerization are controllable by the thermal treatment of the glass, for example,

.the rate of cooling the melt. Thus, there are known the following forms of NaPOs:

(NaPOs) i-sodium monometaphosphate (NaPOa) a-sodium trimetaphosphate (NaPO3) a-sodium hexametaphosphate Quick cooling of a melt provides the hexametaphosphate. Various mixtures of polymers thus obtain asthe cooling is varied. The mono-form is insoluble in water. The triand hexe-forms are soluble in water. Of the'soluble masses.V only the hexa-form is sodium metaof the polyphosphate indicated on the curves.A

'I'he tests were made with Water having 1 gram of CaCl'z per 150 cc. was dissolved at 4 grams in 100 cc. The water was titrated with the polyphosphate solution.

At rst a precipitate occurs, which is then taken up by added polyphosphate. When the precipitate is dissolved, the titration is complete. From the data the amount of calcium sequestered by l gram of the polyphosphate is calculated.

In Fig. 1 curve I0 indicates the sequestering power of sodium hexapolyphosphate. It attains a maximum with increasing fusion temperature, and increasing the temperature does not affect it. Curve I I shows the property for sodiumtripolyphosphate. It has its maximum sequestering power when cooled from about 550 C. High- .er temperatures of melting lessen the power of the resulting product. Curve I2, represents the sequestering power of sodium tetrapolyphosphate. It has a maximum I3 when cooled from about 600 C., falling oif rapidly t0 a low point at 'I4 at about 675 C., then 'rising to a higher point I5, below the said maximum I3 at about '760 C.

The sequestration power for calcium may be diierent from the sequestration power for magnesium. I have found that for calcium sequestration, the power decreases in thesystem from y NaPO3)s to NaAPzO'z, the latter being relatively a poor agent and of practical value only for waters very l'ow in calcium hardness. Yet for `sequestering magnesium, the above given extremes show about the same effectiveness.

For inhibition, much has been published regarding sodium metaphosphates, but I havev The phosphate complex' system from NaPOa to NaiPzOv is about the same as for NaPOs OBJECTIONS T SODIUM POLYPHSPHATES them to utilize their chemical properties are thereby limited. They are extremely water soluble, not in the sense that sugar and salt are soluble, for they do not dissolve that fast. They are however, so soluble that a mass of the product cannot be used to pass water over it for dissolving a minimum amount to eiect the required water treatment. More than is needed is dis` solved, `because of the rate of solution of the glass. With a suitably lower rate of solution, new methods of treatments may be employed.

Another defect is the gelling power of the glasses. When wet with water they lose the granular or glassy form and become gelatinous, causing particles to stick together into a Vsolid mass. Consequently it is not possible, on this account alone, to pass Water through a bed of the material. The rapid rate of' solution is also another handicap to such use.

The sodium polyphosphates in hot water revert quite rapidly to ineffective orthophosphates. On such account certain desirable uses of the agents are prevented, 'and in other uses employ the material ineiiiciently.

When a glassy sodium polyphosphateis powdered, as is desirable to make it a dry powder or a component of a dry mixture, for watertreatment, the powder is so hygroscopic that it causes the mass to congeal, if exposed to water orto water-bearing or hydrated compounds of a mixture, or to a humid atmosphere. As a result of these defects, the application of the sodium polyfphosphates for treating water, is limited .largely to dissolving the glasses and adding the solution to the water to be treated.

'Ihese defects are not only true of sodium polyphosphates, but of potassium polyphosphates and other alkali metal polyphosphates. Because of these defects common to alkali-metal polyphos phates, and because of the less expensive sodium lust sumcient oi' the agent to eect the desired treatment. and they bed retains its granular form, requiring only renewal by adding more of the granular compound to replace that dissolved.

According tothe present invention in the broadest aspects, new compounds may be prepared which have objectionable -features like the sodium polyphosphates, yet which have greater powers of sequestering or inhibition, or both, and diierent combinations of/such powers for calcium and magnesium. In other words, the invention not only permits making vcompounds with improved chemical properties over the prior arf; so-v dium polyphosphates, and with the same character of objectionable physical properties, but it also permits making compounds with the same character of advantageous chemical properties and without the disadvantageous physical properties, considered singly or in combinations. Various degrees of combinations of these improvements are possible within the scope of the present invention.

For convenience in simply explaining the present invention the compounds are represented as containing three basic ingredients, whereby the scope of the invention may be graphically illustrated on triangular coordinate charts. The in'- gredients are:

(2) Alkali metal oxide, such as NazO or KzO (3) Metal oxide, such as MgO, CaO, SrO, BaO,

A1203 and F8203 However, in order ybetter to study and explain the base, .practicallyfthe art has been developed and.

studied. to use the sodium polyphosphates.

Attempts have been made heretofore to overcome some of these objectionable properties. especially to overcomehygroscopicity. Coating the particles with a sodium phosphate or intumesced borax have helped somewhat (see U; S. No. 2,008,561 and No. 2,024,543), but these only -add surplus chemical to the'treated water, be-

yond that required for sequestering or inhibition.-

IMPROVE!) PoLYPHosPnATEs `of the composition, the hygroscopicity and the the water-soluble vitreous phase.

rate of solution maybe controlled, and the gelling Y may be controlled or stopped. Thereby, new

,methods of application of the polyphosphates have been opened up, and new mixtures are permitted. For example, a granular bed of a chosen composition may be used to pass water through it, at a controlled rate, so that the water dissolves eil'ect of variables, it has been considered best to study the simple systems, as will vbe apparent hereafter.

In carrying out the invention, any composition to provide the desired ratio of the oxides desired. is fused until molecular dehydration is complete.

IThe temperature is such that a complete fusion occurs and such that upon quickly cooling a clear vitreous glass results. overheating has no bad e`ects. Cooling small masses quickly is readily accomplished and assures clear glasses. By slow ing the rate of cooling, crystallization can occur. A small amount of crystallization may destroy clarity. giving an opalescence or cloudy`- eilect, caused by inclusion of water-insoluble crystals in The crystal portion is notof value and hence such cloudiness is preferably avoided, or accepted when not so great as to impair the efficiency of the compound.

By making many compounds, testing their physical and chemical properties, and plotting the successful compounds on triangular coordinate paper, I have found that a definite relation exists. Just as there is a range of composition between 100% NazO and 100% P205 including the intermediate mixtures, in which range the intermediate range from NaPOs to Na4P2Ov represents the water-treating sodium polyphosphates, there is also a like range for other metals. Thus for the bivalent metals, Ca, Sr,'Ba and M82. represented hereinafter by M", there is a range of M"- vpolyphosphates from M"(PQ3) to Mz07. For the trivalent metals Fe and .A1, represented here- Afound that when a triangular coordinate chart is made at which one vertex represents meta1 being hereinafter represented by A, and its oxide being A20; another vertex representing 100 molar percent of P205, and the third vertex representing 100 molar percent ,ofthe metal oxide M"O or M"'2O3, I may connect with straight lines the corresponding terminals of the A-polyphosphate range and the respective M-polyphosphate ranges, as boundaries for the respective areas of the chart in which lie the compositions of the invention. Thus, I have found that the compositions may be considered analytically as corresponding to a product made from A-polyphosphates and M-polyphosphates, without commission to the proposition that such definite compounds are present as such and independent of each other.

I have found that the M-polyphosphates do not possess 'water-treating qualities, and that new compositions only lose practical yalue as water treating agents when the solubilityy becomes limited for some practical usage. approaches the line of M-polyphosphates in the chart referred to, the water-solubility decreases, and other properties change, so that considering the practical utilities of the compositions from one or more particularly useful properties, there are practical limits of composition for the'preferred and practical complexes. However, these are not necessarily functional limits, nor limits of the invention. The invention therefore contemplates broadly those new complexes which are either water-soluble, or too water-insoluble, to function practically. 'I'heinvention also contemplates, and more specically, limits for preferred compositions dictated by actual observations on the property values.

These practical limits are variable according to the specific character of the metal M. When M is trivalent, the molar percent of M"2O3 is preferred not to exceed 5% in order to provide a practically valuable water-treating agent. Where the metal M is magnesium, the molar percent of MgO is preferred not to exceed for the same reason. Where the metal M is alkali earth metal,

the molar percent is preferred not to exceed 17.5% for the same reason.

When there is but a slight amount of metal As the complex- (M) oxide in the new compositions, an improveso obviousl or detectable for small usages of metal M. Where an important property, or a combination of several properties, is apparent at some low content of metal M, that is taken as a lower limit for the preferred practical complexes. I have determined that in the case of using an oxide of M the improvements 'over sodium polyphosphates for water-treatment are of generally practical utility when the molar percent of M"'2O3 is as low as 1%. and when the molar percent of M"O is as low as 2.5%. However,-I do not exclude from the scope of the invention complexes having M- oxide below these preferred practical limits.

I have represented the extent of the improvements in Fig. 2, upon a triangular coordinate graph. 'I'he vertex 20 represents alkali-metal oxide in molar percent of 100. The`vertex 2l representsPzOs in molar percent of 100. The vertex ture.

22 represents oxide of metal M" or M'" in molar percent of 100.

Point 23 represents the complex APOs such as NaPOs.

Point 24 represents the complex A4Pz07 such as Na4P207.

Point 25 represents the complex M(P0a) 2.

Point 26 represents the complex M"2P2O'z.

Point 21 represents the complex M'(PO3)3.

Point 28 represents the complex M"'4(Pz0'1)3.

Line 23-24 represents the alkali-metal polyphosphates of the prior art.

. Lines 25-26 and 21-28 represent the locations on the chart for polyphosphates respectively of MII MII.

Lines connecting the terminals of the ranges of the M-polyphosphates to the range of alkalimetal polyphosphates are drawn and are designated 29, 30, 3| and 32. m

Lines 29 and 3D form a zone on the chart in which lie the complexes of the present invention involving M'" metal, or Fe and Al. In this zone I have found that line 33 generally denes the upper limit for the preferred practical watertreating complexes, at about 5 molar percent of the oxide of iron or aluminum in the complex. Dotted line 34 in this zone defines the line of lower molar percent, at about 1%, of oxide of iron or aluminum, where the benefits of its presence are obviously apparent and sufficiently practical to warrant using compositionslying on the line 34 valent metal M", of which the alkali earth metals Ca, Sr, and Ba form one class and Mg forms another; In this zone I have found that line 35 generally defines the upper limit for the preferred practical water-treating complexes, of about 15% l molar percent of MgO in the complex. The like limit for molar percent of oxide of Ca, Sr, or Ba is about 17.5%, represented by line 36 in the M"- 'zone between lines 3| and 32.

Dotted line 31 in this zone defines the line of lower molarpercent, at about 2.5%, of oxide of Mg, Ca, Sr, or Ba, where the benefits of its presence are obviously apparent and sufficiently practical to warrant using compositions 4lying on the line 31 for water-treating. I do not intend to exclude from the scope of the invention complexes lying between lines 31 and 23--24 in the M"zone, the preferred and practical water-treating compositions lying in the M"zone between the line 3l and the lines 35 or 36.

ALxALr-METAL i Heretofore the alkali-metal polyphosphates -have been practically limited to sodium. Potassium may be used, but its compounds are higher melting and therefore more costly to manufacalkali-metal is used, I contemplate both single and mixed alkali metal, suchA as the preferred sodium alone, or sodium and potassium mixed. I prefer the oxide of potassium not to exceed 50 molar percent of the mixtre of oxides of sodium and potassium, for one reason, to keep the fusion point lower and thereby to reduce cost. In addition to these reasons, I have found that in some In the present invention, where the term cases. the desired properties decrease when the molarratio oiKnOtoNazO exceeds 20 to 80.

I haveA made complexes wherein all the .alkali metal oxide is X20, and wherein various ratios of Naso to Kao have been employed, and although they have substantially the same chemical properties for treating water, the physical properties vary. Inf the particular series tested, as later illustrated, the improvement of lower hygroscoplcity of the complex begins to be lost where the KaO begins to exceed the NaaO.

. .Fusion A In making the complexes various materials may be combined and heated to fusion, reaction becoming .complete when any required dehydration is completed and a melt is.obt ained which can be quickly chilled to avitreous mass, Oxides and carbonates of the alkali metals and of the metal M may be used, vand phosphoric acid, phosphorus oxides, alkali or other metalvphosphates or polyphosphates, so long as the ix'ntial ingredients are suiiicient inv quantity to provide the desired residue. It is preferred to heat above the melting point to insure a crystal-clear glass on chilling.

. muets 1.

A mixture consisting of 23.0 grams C. P. 85%

' mP0l,5.84 grams C. P. NaOH, and 1.62 grams 97% MIS(OH)2 was heated with gradual rising temperature and was held for one hour at 800- 1 850 C. The clear liquid melt was cooled qllickly with the resultant formation of a clear Aglassy material of the molar ratio: 13.5% MgO, 36.5% Nano, and 50% P205. This compound is a mixed metal metaphosphate, analytically corresponding to 84.4 molar percent of NaPOa and 15.6 molar percent of Mg(POs)2 or by weight, 75.2% NaPOa and 24.8% Mg(POs)2. n the chart of Fig. 2, it falls at thepoint designated 40 on line31,

EXAMPLE 2 .ing to the present invention complexes may be made which have a low rate of solution, a high solubility, and ,no tendency to congeal.l

To illustrate these properties reference ismade to a series of complexes prepared in to 20 mesh granulation. In a vertical tube to form a bed l inch in diameter and 1.25 inches high, containing grams of a complex, cold water was passed at the average rate of 100 cc. per minute for 4 hours. The amount of complex dissolved 'was determined by analysis of the discharge for P205, expressed' as parts per million (P. P. M.)

'P205 'dissolved by thewater. The compositions of the series were according to Table 2, which also gives the P. P. M. P205.

Table 2Rate of solutio'n Molar ratio n R M. Item P305 diS- Mg N310 P50. Solved A 0.5 43.5 50.0 90.0 13.5 36.5 50.0 as 1.0 46.5 4&5 120.0 -la4 423 42.3 z5

Table 2 shows that 'the higher content of MgO greatly lowers the rate of solution. Items 2 and 4v with a low rate of solution retain their granular form without congealing or swelling, and become dry when exposed to air. All the items permit making a 25% solution. The rate of solutionV lvaries with the composition of the complex. By changing'the MgO to FesOa or BaO, about onethird and live-fourths respectively of the molar amount for MgO is required for the same eiectiveness in securing low rate of solution.

The items 2 and 4 having low rate of solution are within the practical range of eilectiveness for 40 inhibition action, and because they do not con- A mixture consisting or 23.0 grams o. P. 85%

HsPOl, 7.60 grams C. P. NaOH, and 0.78 gram.

ANCH); was heated as in Example 1 and held for one hour at '900 C. The clear liquid melt was cooled quickly with the resultant formation of a clear glassy material of the molar ratio:

2.5% Altos, 41.5% Nalo, and 50% P205. This is a mixed metal polyphosphate, analytically corresponding to a product made from 2.45 parts A1203, 29.0 parts NazO and 68.5 parts P205 by weight. On the chart of Fig. 2, it falls at the point 4|, the junction of line 31 and line 3|.

VFrom the above examples, it is seen that point 40 falls on the boundary line 3| .0f the zone for its complex, and that although point `4| lies also on line 3|, it falls within the corresponding boundary line 29 for the zone of its complex.

In the following discussions of properties of the I 'Sodium polyphcsphates'of the prior art have a very high rate of solution and high total solubility. In 4addition they tend` to congeal into geal, they may be used as filter beds for owing water over the material in treating the water. Other new uses are permitted which likewise have been impossible heretofore, when only the sodium polyphosphates have been available.

It may be stated also that as the alkali-metal content of the complex increases, the desirable physical property values decrease. The preferred complexes lie on or near the lines 29 and 3| lbounding the composition zones.

The chemical utility of the complexes for treat- .ing water is retained so long as the complex is soluble. As the content of metal M increases,

and as the content of alkali metal decreases, the I solubilities decrease, as a general rule, exemplified more particularly hereinafter by detailed discussion of the MgO-NaaO-PzOs' system.

. In the areas of Fig. 2 from line 23-24 of the sodium polyphosphates, to the preferred practical limits of lines 33 for M'", line 35 for MgO, and

lille 36 for the alkali earth metals, all the complexes are soluble 'to form 25% solutions in water.

masses when wetted. Accord- I In Fig.- 2, the point 43 represents the composition with molar percentages of:

. Per cent M l -30 4NaiO 20 P205 A5() This compound ls practically insoluble ln water,

and in 'dilute and concentrated hydrochloric acid or nitric acid. Yet it is perceptibly soluble in water as shown by the right end' of the graph of Fig. 8. The term "water-soluble includes any solubility atall, because mere traces in solution are highly eiective. A s the composition may be varied on the line of constancy for MgO to increase the NazO content at the expense ofPaOs. the solubility becomes more preceptible. Also as the composition may be varied from point Il on line 3|, the solubility becomes more perceptible, u'ntil at the junction of lines 3i and I5 it is extremely useful and in the preferred practical eld. 'I'he change from solubility to-insolubility is gradual and does not permit of defining a limit except in terms of some arbitrarily selected limit. When absolute insolubility isI present, the complex is not useful for water treatment. Where a useful solubility is present, the complex may be employed for Water treatment. Therefore, I designate'the complexes within the scope of the present invention, whichhare useful for water treatment, as .those vitreous glasses consisting analytically of the dened mixed-metal polyphosphates, which are water-soluble.

'HYGnoscoPIcIrY Crystalline sodium metasilicate Crystalline trisodium phosphate MSO 6.5 moles Polyphosphate complex NaaO 43.5 moles P505 50.0 moles I the mixture is stable and unaected by such conditions, vand. has the same chemical properties as the caking mixture, for example when used as a water-softening dish-washing compound.

The improvement in decreased hygroscopicity is further evidenced by a series of complexes exposed to air for 2 hours at 851 F. of 65% relative humidity in a humidity-control cabinet. 'I'he re- Srsmrrx The polyphcsphates oi the prior art and oi the present invention revert in water to orthophosphates, which lack the valuable water-treating properties. The rate of reversion in cold water is slow, permitting practical use of cold water solutions. In hot water, the prior art sodium polvphosphatesrevert rapidly makina them less eiiicient ior use to prevent scale in boilers and heat-exchangers. At 100 C.. the rate oi reversion is soiast, that they are generally considered unstable. l,

The complexes of the present invention are much vmore stable in hot water solutions. 'Ihey retain their unique properties for a longer period `in hot waterthan theprior art sodium polyphos- Table l-Stilbili Molar ratio of complex rmt verdon 1 Mg0 NMO P105 1 hour 2 hours 5 hours 7 hours From a plot oi' these data it may be seen that atabout7and4hoursthenewcomplexhasthe status of the old at about 3 and 2 hours respec- 40 tively and Valso that theV rate of reversion is much lower. Thus. the new complexes 'are more emcient lfor hot waters. and also permit ci uses heretotore not practicable.

. Inrnnrrxon v The use of polyphosphates to prevent precipisults are shownin'lable 3. tation o i' calcium and magnesium compounds Table-Hyaroscopicity -M olar ratio Per mt Item gainin Mgo cao sro Bao 1.0. r5.0 Nuo no, H80

50.0 50.0 1.4 a5 42.9 sae 005 as 41.5 50.0 1.a 10.0 40.0 50.0 0.50 ias 55.5 50.0 0.13 40.0 50.0 das 33.5 w muy 4u 500 ma 30.5 50.0 0.35 v 4st 50.0 2.05 40.0 50.0 0.55 ses 500 0.20 62.5 37.5 11.0 50.6 38.1 5.5

menerel it is shown that as the tol-.s1 mais:

. metal oxide content increases, the hygroscopicity increases. Items I and I3 are sodium polyphosphates of the prior art, and show by contrast the metal M, it is possible to control from the hardness constituents o! waters containing such hardening ions, is practically limited to the use 'of only a few parts ofthe polyphosphates per million parts'oi water. The complexes of the present invention have this power of inhibition to high degree, and this power is also present in complexes falling within the polyphosphate zones M" and M'" of Fig. 2, beyond the limiting lines 33, 35 and I5 already described. For inhihygroscopicity. l5 bition uses such complexes beyond these lines are considered t reu within the broad scope of the present invention, but the preferred complexes lie in the areas expressed as preferred, because of their valuable combinations of properties, such as'low hygroscopicity, low but useful rate of solution and stability. whereby they are more universally useful.

The value of the complexes for inhibition is evidenced by the results given in Table 5. Water n containing' calcium bicarbonate as the hardness agent, in amount .equivalent to a hardness of 1000 n.1. M. of ceco; was treated with 2 P. P. M. of the complexes shown in the table, and held for one hour at 80 C., which conditions normally induce precipitation of CaCOa. The amount of precipitation was determined and is given in Table as percent of total hardness precipitated.

Item 5 shows that no treatment causes about half the calcium to precipitate, and item 1 shows I that the prior art sodium polyphosphate reduces this to 21.5%. The new complexes of items 2, 3 and 4 reduce this still further, and therefore evidence greater power for inhibition under' these cond1tions. SaQUEsrRArroN That union of calcium or magnesium ions of hard water with a polyphosphate, which prevents reaction of the ion with soap, that is the action of sequestration, is as characteristic of the new complexes as of the prior art sodium polyphosphates. It is shown below that a. magnesiumsodium-polyphosphate changes little in its high sequestering powerfrom about 0 to A10% molar ratio of MEO.' starting from thesodium metaphosphate variety. But as shown above the hygroscopicity decreases as the'MgO content increases, such that at Amolar percentof MgO, it' is useful in a dry powdery dish-washing coinpound. Inother cases, the complex may be selected for some desirable physical property.

The eectiveness of the new complexes, compared to a prior art sodiumpolyphosphate, is evidenced in Table 6. A liter of water containing 13.5 grams of hardness as CaCOa, was treated with varying amounts of numerous new complexes until the' water was fully softened against soap. The amount of the complex so, required is Item 1 represents prior art, and it is seen from items 2 and 3 that the sequesterlng property is not altered by the MgO content. All the complexes are of the same order of utility Vfor sequestering. Thus a complex may be selected having the most favorable physical properties for the use intended.

Aixam-METAL Oxma The eiect of changing all or part of the NazO of the new complexes, to KzO is illustrated in Table 7. A deinite formulation has been chosen in which the molecular ratios of MgO, P205 and alkali metal are xed, and the alkali metal is progressively changed from all NaaO to all KzO. The measured eiect is hygroscopicity, given as the gain in percent by weight of water in 2 hours at 90 F. at 65% relative humidity, using granular materialof substantially the same neness.

' Table -Nazo-Kzo Molar ratio oi complex I Iygroscq- Item pxcity. (gam in percent M P105 N050 KzO- water) The iive items above possess substantially the same value for inhibition and sequestration, and until X20 begins to predominate the alkali-metal oxide component, the hygroscopicity remains low.- 'I'he preferred compounds therefore have atleast 50% of the' alkali metal as NazO. e

SELECTION or COMPLEXES THE PoLYPHosPHATE SYSTEM McO-NAzO-PzOs i Numerous complexes in this system have been selected to demonstrate the variations in properties. -In Fig. 3,'a portion of Fig. 2 has been reproduced With the same indicia. The lines 23-24, 3l and 32 outline themore luseful end of the zone for the system. Line 28-24 is the line of prior art polyphosphates. Line 50 repregiven in the table. 00 sents series A of complexes, the properties of Table 6-Sequestratzon Molar ratio of complex Gms Item required Mgo cao sro Bao Feeoe A1203 Nalo no. ne

1 50.0 50.0 1.00 2 4.5 45.5 50.0 1.00 i 10.0 40.0 50.0 1.00 4 10.0 40.0 50.0 1.00 5--.---- 100 40.0 50.0 1.00 e 10.0 40.0 50.0 1.00 7- 2.5 47.5 50.0 1.00 s 13.5 Y 30.5` 50.0 2.40 9. aas 50.0 2.40 m a5 42.0 53.5 2.00 n 025 37.5 2.00 12 025 50.0 40.15 2.40 1s as 1 50.0 42.0 aoo which are illustrated in other figures. Table 8 gives the formula for series A, and for other series B, C and D, identifying the series and formula with lines 50, 52 and 3| `in Fig. 3.

Table 8 In Fig. 3

Ratios in complex Series Line A 50 Molar Mg0==molar Naro-'50 B 5l Molar Naz0=50 C 52 Molar P20s=molar NagO D 3l M0181' Pz05=50 In graph-form figures about to be described, the complexes are identified by the series indicia, from which the composition may be determined by reference to the graph and to Table 8. y

Fic. 4 Hxcaoscorrcrrv Series A, B, C and D, and prior art complexes, have been ltested to determine the gain in weight by adding water, in 2 hours, at 85 F. at 65% relative humidity. The percent gain in weight is plotted vertically in Fig. 4. Horizontally, the molar percents of MgO for the series A, B, C and D are plotted, giving the curves respectively 55, I

56, 51 and 58 for the said series. Point 59, common to the curves represents the hygroscopicity ofthe complex of point 23 in Figs. 2 and 3, of sodium hexametaphosphate. Point represents another sodium vpolyphosphate of composition at point 6| on Fig. 3.

Line v59-60 in Fig. 4 represents the hygroscopicity of complexes on 4the line 23-'6I in Fig. 3,.V Lines 55, 55, 51 and 58 represent the hygroscopicities of complexes respectively on lines 50, 5|, 52 and 3| in Fig. 3. The composition lines in Fig. 3123-24, 50, 5|, 52 and 3|, and the hygroscpicity lines: 59-60, 55, 56, 51 and 55 in Fig. 4 follow a corresponding generally fan- Fis. 5` SnQUnsrmmoN In Fig. 5 has been plotted vertically the grams of complex required to soften against soap, 1 liter of water having 13.5 grains of hardness as CaCOa.

Horizontally, has been plotted the molar percent of MgO in the complexes of series A, B, C and D. Point 63 represents the sequestering power of sodium hexametaphosphate of point 23 in Fig. 3.

Lines 64, y65, 56 and 51, represent the amount of complexes of the indicated series required to soften thcwater.

The curves follow a system in definite order with the fan-shaped pattern in Fig. 3 of lines 50,

5|, 52 and 3|. It is shown that within certain limits, for example up to 10 molar percent of MgO on line 3| in Fig. 3, or up to point 58 on said line,

the new complex is fully as emcient as sodium v hexamethaphosphate, an important difference being (see Fig. 4) that the new complex (point 58) is practically non-hygroscoplc.

FIG. 6; INrrrrsnroNy In Fig. 6 is plotted vertically the amountfof CaCO: precipitated from a waterhardened with calcium bicarbonate, of 1000 P.'P. M. CaCOa, by heating for 1 hour at 80 C. in the presence of 2 P. P. M. of a complex. Horizontally, is plotted the molar percent of MgO in the complex. The line marked 10 is the amount,l as a range, which is precipitated when no complex is added. Consequently, the lower the curves in the plot, the more eflicient is the complex for inhibition under the described conditions. Curves 1|, 12, 13 and 14 respectively represent the results for series A, B, C and D.

Series D falls on line 3| in Fig. 3, and it shows that the inhibiting power graduallyl improves as the MgO content increases, being ,constant from about 14 to at least 30 molar percent. For series A, the inhibiting power has maximums greater than for series D. The pattern ofthe curves up to about 5 molar percent of MgO follows a definite order of a fanlike pattern like the series lines in Fig. 3. A11 thecompositions shown are better than sodium hexametaphosphate, found at point 15 in Fig. 6 and point 23 in Fig. 3.

COMPARISON or SYSTEMS VARYING M In Fig. 7, al comparison of systems has been made as to hygroscopicity, on complexes of nearly the same order,-varyirrg in the metal M. The

` complexes compared are the sodium-M-polyphosphates. Where M is divalent, the metaphosphates on line 3| of Fig. 2 are used. Where M is Fe the -metaphosphate on line 2 9 of Fig. 2 is used. Where M is A1 the polyphosphates on line 3| of Fig. 2

are used.

scopicity of sodium-aluminum polyphosphates,

falling on line 3| in Fig. 2. Point 82 represents the hygroscopicity of a 'lsodium-iron-metaphosphate, falling on line 29 in Fig. 2.

These show that the trivalent metal M is more effective to lower hygroscopiclty than divalent metal M, and that for this function the divalent metals Mg, Ca, Sr, and Ba are substantially equivalent.

SoLUBILrrY As stated above the term solubinty compie- --hends rate of solution and amount of material capable of being dissolved iny a given amount of water at a given temperature. A precise value for the latter property is. a characteristic of many chemical salts. However, there are other factors which sometimes make Ait dimcult to determine tOtal SOlllbility Orto determine if there i8 a total solubility. l

The glasses of the present invention oer Vauch obstacles. As stated above there is a reversion reaction which is slow at low temperatures and more rapid at elevated temperatures. It has been shown that the glasses exhibit varying rates of solution. It is readily to be understood that conditions may exist such that the rate of reversion the contents of Na20 and MgO are varied.

Using a temperature in the range from 25 to 30 C., the effects of composition, iineness of division, amount of solid in contact with water, and time of contact with water, have been studied as factors involved in dissolution of the glasses in water.

Fig. 8 shows a curve 85 representing the concentration of solution produced, using powdered material passing a, 60-mesh screen, in the quantity of 100 grams of solid per 100 grams of water under standardized conditions for 10 hours. The glass composition was varied so as to show the eilect of increasing content of MgO upon the concentration of solution thus obtained. vAt about molar percent of MgO, it is seen that the solubility, as plotted in terms of grams of dissolved glass in 100 grams of solution, begins to drop. Thus, for making solutions to be added to water, the more soluble forms up to about 15% are preferred, When water may be allowed to ow through a bed of glass. a higher content of MgO may be present advantageously. Y

In Fig. 8, the expressed solubility at 30 molar percent MgO is 2.47 from the 60-mesh glass..

Where glass of the same composition was used, which passed a 200-mesh screen, the expressed solubility was found to be 3.39, showing greater neness aided dissolution.

Using glass of the 30 molar percent MgO which passes a D-mesh screen, the quantity exposed for 10 hours was varied showing results as follows: l

Expressed Quantity exposed to 100 grams water solublhty WOO Expressed Hours exposed solubility All of these results show the desirability of ilowing water through a bed or over a bed of the divided glass, controlling rate, composition, and contact, in order to secure the desired addition of the treating agentA to the water involved. Some compositions may be dissolved in a few minutes, others not. A complex of 20 molar percent MgO at 60-mesh granulation with an equal weight of water will form a solution in 10 hours, but it is practically impossible to obtain complete solution of 1 gram of a complex of 15 molar percent MgO in 100 grams of water in 10 hours at 25 C. The circumstances of use will determine what type of composition is to be selected for its solubility characteristics in such use.

'I'he complexes of the present invention appear to have an almost infinite solubility with a rate of solution decreasing as the eilective M isincreased.

The use of such slowly solublecomplexesin other iields, such as for fertilizers, takes advan-g compositions, as well as many of the rapidly soluble ones, lare 'characterized -by no scopicity.- This is another valuable property -fo'r lo fertilizer use. Theglasses may be used primarily with or without calcium as the metal M. Thus, it is possible to make a glass complex within the present invention which provides phosphate with potash, or with lime, or with both, which is nonence is made to my copending application, Seriall No. 519,633, filed January25, 1944, as a continuation-in-part of the present application and of sa'id Serial No. 402,725, which serial No. 519,633 is directed to certain water-treating compositions and methods involving the aluminum compositions of the present disclosure.

I claim: 1. A'homo'geneous vitreous material as a glassy water-soluble fusion product consisting analyti; cally of the oxides: A20, P205 and MO wherein A20 is alkali metal oxide, M0 is oxide of dlvalent metal M, and M is metal selected from the group 40 consisting of magnesium, calcium, strontium and barium, the P205 being present to an extent in the range from 331A; to 50 molar per cent of the total molar content of said oxides, the MO being present to an extent in the range from 2.5 to 17.5 molar per cent of said total molar content, and

the A20 being present to an extent ranging upwardly from 32.5 molar per cent of said total molar content. A

2. AV homogeneous vitreous material as a glassy water-soluble fusion product consisting analytically of the oxides: A20, P205 and M0 wherein A20 is alkali metal oxide, M0 is oxide of dlvalent metal M, and M is metal selected from the group consisting of magnesium, calcium, strontium and barium, the .P205 being present in the range from 33% t0 50 molar percent of the total molar content of said oxides, the M0 being present to an extent in the range from 2.5 to 30 molar per cent of said total molar content, and the A20 being present in quantity ranging upwardly from 20 molar per cent of said total molar content.

3. A homogeneous vitreous material as a glassy water-soluble fusionproduct consisting analyti-j)i cally of the oxides: A30, P205 and M0 whereinf A20 is alkali metal oxide, M0 is oxide of divalent metal M, and M is metal selected from the group consisting of magnesium, calcium, strontium and barium, the composition being dened by the area of a trilinear diagram of molar content of said oxides which area is bounded -by the lines as follows: the line of 2.5 molar per cent of M0; the line of 50 molar per cent of P205; the line of 20 molar per cent of A20; and the line of 33% molar per cent of P205.

4. A homogeneous vitreous material as a glassy tage of the slowness of dissolution. Such useful to dispense P205 to soil. Also, they may" have K20 in whole or in part as the alkali metal oxide.

.water-soluble fusion product, consisting analytiextent rangingy upwardly from 35 cally of the oxides: A20, P205 and M wherein A20 is alkali metal oxide, M0 is oxide of divalent to the .third side 0f the diagram by the line of' about 20 molar per cent A20, which latter line intersects the line of 50 molarper cent of P205 at about 30 molar per cent of M0.

5. A homogeneous vitreous material as a glassy water-soluble fusion product consisting analyti cally ofthe oxides: .Na20, P205 and MgO, the P205 being present in the range from 331/3 to 50 molar per cent of the total molar content of said oxides, the MgO being present to an extent in the. range from 2.5 to molar per cent of said total molar content, and said Na being present to an molar per cent of said total molar content. y

6. A homogeneous vitreous material as a glassy water-soluble yfusion product consisting analyti- 4cally of the oxides: Na20, P205 and MgO, the

P205 being present in the range from 331/3 to 50 molar per cent of the total molar. content of said oxides, the MgQ being present to an extent in the range from 2.5 to molar per cent of said total molar content, and said Na20 being present in quantity ranging upwardly from 20 molary per cent of said total molar content.

7. 'A homogeneous vitreous material as a glassy water-soluble fusion product consisting analytically of the oxides: NazO, P205 and MgO, the composition being 4dened by the. areaof a trilinear. diagram of said oxides which area is bounded `by the lines as follows: the line of 2.5

" and the une of 331/', molar per cent of P205.

.8. A homogeneous vitreous material as a glassy water-soluble fusion product consisting analytically of. the oxides: Na20, P205 and Mg0, the

is bounded by lines parallel to one side of the diagram and corresponding to 331/3 and 50 molar per cent of P205, said area being bounded parallel to a second side of the diagram by the line corresponding to 2.5 molar percent of MgO, and

being bounded parallel to the third side of the diagram by the line of about 20 molar per cent 4of N220, which latter une intersects the line of 50 'molar per cent of P205 at about 30 molar per cent I P205 being present to the extent of substantially 50 molar per cent-of the total molar content of said oxides, the MgO being present to an extent in the range from 2.5 to about 30 molar per cent of said total molar content, and the NazO correspondingly being present to an extent ranging upy wardly from about 20 molar per cent of said total molar content.

10. A homogeneous'vitreous material as a. glassy 'from the group consisting of calcium, strontium and barium, the P205 being present to an extent in the range from 331/3 to 50 molar per cent of the 4total molar content of said oxides, the MO being cally of the oxides: Na20, P205 and CaO, the

B205 being present in the range from 33% to"50 molar per cent of the total molar content of said oxides, the CaO being present to an extent in the range from 2.5 to 17.5 molar per cent ofthe saidl total molar content, and the Na20 being present to an extent ranging upwardly from 32.5 molar per cent of said total molar content. r

. CHARLES S. KING. 

